TW201920028A - Glasses with improved tempering capabilities - Google Patents

Abstract

The disclosure relates to glass compositions having improved thermal tempering capabilities. The disclosed glass compositions have high coefficients of thermal expansion and Young's moduli, and are capable of achieving high surface compressions. A method of making such glasses is also provided.

Description

Glass with improved tempering ability

This application claims the priority right of U.S. Provisional Application No. 62 / 549,507 in accordance with the Patent Law. This U.S. Provisional Application was filed on August 24, 2017. Reference forms are incorporated herein.

This case discloses a highly temperable glass composition. More specifically, the disclosure of this case is about a glass that has improved tempering compared to general soda lime glass. Even more specifically, the disclosure of this case is about a glass composition having a high thermal expansion coefficient and a high Young's modulus for use with a thermal tempering process.

In thermal tempering, the glass product is heated to near the softening temperature and then quenched rapidly. As a result, the glass will have a lower surface temperature than the interior during cooling. The temperature difference is maintained until the glass surface is cooled to room temperature. Because the center of the glass cools more slowly to room temperature, the center of the glass shrinks to a smaller specific volume, while the high specific volume of the surface layer remains unchanged. This results in a surface compression layer that imparts strength to the tempered glass. The difference in specific volume is mainly due to the difference in thermal expansion of the glass once it has cooled, and to a lesser extent due to the virtual temperature difference between the surface and the bulk. For the first approximation, the stress distribution in hot tempered glass can be represented by a simple parabola, and the magnitude of the surface compressive stress is approximately equal to twice the central tension.

Thermally tempered glass (sometimes called safety glass) is commonly used in situations where safe fracture performance is required to prevent damage in the event of failure, to strengthen the side and rear windows of automobiles, and for example shower doors object. It is expected that when thermally tempered glass breaks, unlike annealed glass, the thermally tempered glass will shatter into rock salt-like fragments that do not have sharp edges or needle-like shapes. Therefore, it is important to characterize the fracture behavior of hot tempered glass. The desired fracture behavior is called "dicing" and occurs when the glass has reached full tempering.

In addition to the safety aspects of thermally tempered glass, tempering strengthens the glass, making it more resistant to damage and durable. Due to the increased durability, tempered glass can be used in applications where general glass breaks quickly-for example, automotive windshields where the glass may be impacted by rocks or other hard materials. Due to the increased use of glass in architectural, automotive, and electronic device applications, there is a continuing need for strengthened glass with improved tempering capabilities.

In the following description, whenever a group is described as including at least one of the components of a group and a combination of those components, it should be understood that the group may include any number of the described components, It consists essentially of, or consists of, any number of the mentioned components, either individually or in combination with each other. Similarly, whenever a group is described as consisting of at least one of the components of a group or a combination of those components, it should be understood that the group may be composed of any number of the recorded components, whether they are Alone or in combination with each other. Unless otherwise specified, when a range of values is recited, the range of values includes both the upper and lower limits of the range, and any range therebetween. As used herein, unless otherwise specified, the indefinite article "a" and the corresponding definite article "the" mean "at least one" or "one or more". It should also be understood that the various features disclosed in the description and the drawings can be used in any and all combinations.

Where numerical ranges (including upper and lower limits) are noted herein, unless otherwise stated in a particular case, it is desirable that the range includes the endpoints of the range, and all integers and fractions within the range . It is not intended that the scope of a patent application's scope be limited to the particular value recorded when the scope was defined. In addition, the equivalent, concentration, or other value or parameter is given as a list of ranges, one or more preferred ranges, or upper and lower preferred values, and should be understood as a particular disclosure by any pair of any range All ranges formed by the upper limit or better value and the lower limit or better range of the range, regardless of whether the pair is disclosed separately. Finally, when the term "about" is used to describe a range value or endpoint, the disclosure in this case should be understood to include the particular value or endpoint referred to. When a value or endpoint of a range is not recorded with "about", it is desirable that the value or endpoint of the range includes two embodiments: one modified with "about" and one not modified with "about."

As used herein, the term "about" means that quantities, sizes, recipes, parameters, and other quantities and characteristics are not and need not be precise, but can be approximated and / or larger or smaller as desired to reflect tolerances , Conversion factors, rounding, measurement errors, and the like, and other factors known to those of ordinary skill in the art to which this invention belongs. It should be noted that the term "substantially" may be used herein to indicate inherent uncertainties that may be attributed to any quantitative comparison, value, measurement, or other representation. These terms are also used herein to indicate the extent to which a quantitative representation may deviate from the referenced object, but will not cause the basic function of the subject in question to change. Thus, "non-Al ₂ O _3" in which the glass is not added positively supply or batch Al ₂ O ₃ glass to glass, however, the Al ₂ O ₃ may be a very small amount, present as an impurity (e.g., 500, 400, 300, 200, or 100 parts per million (ppm) or lower).

Unless otherwise specified, all compositions are expressed as mole percentages (mol%). Unless otherwise specified, the coefficient of thermal expansion (CTE) is expressed as 10 ^-7 / ° C and represents a value measured over a temperature range of 25 ° C to 300 ° C. Low temperature CTE (LTCTE) is measured at 25 ° C and expressed as 10 ^-7 / ° C. High temperature CTE (HTCTE) is measured at 300 ° C and expressed as 10 ^-7 / ° C. The sum of LTCTE and HTCTE is expressed as 10 ^-7 / ° C. Density in grams / cm ³ is measured by the Archimedes method (ASTM C693). Young's modulus, shear modulus, and Poisson's ratio are measured by ASTM C623 standard. Glass composition

In thermal tempering, the glass product is heated to near the softening temperature and then rapidly quenched. As a result, the glass will have a lower surface temperature than the interior during cooling. Keep the temperature difference until the glass surface cools to room temperature. Because the center of the glass cools more slowly to room temperature, the center of the glass shrinks to a smaller specific volume, while the high specific volume of the surface layer remains unchanged. This results in a surface compression layer that imparts strength to the tempered glass. The difference in specific volume is due to the combination of the difference in thermal expansion of the glass once it has cooled, and the virtual temperature difference between the surface and the block. For the first approximation, the stress distribution in hot tempered glass can be represented by a simple parabola, and the magnitude of the surface compressive stress is approximately equal to twice the central tension.

When thermally tempered glass is broken, unlike annealed glass, the thermally tempered glass will shatter into rock salt-like fragments that do not have sharp edges or needle-like shapes. This behavior is particularly useful in situations where a safe fracture surface is necessary, and for this reason, it is critical to characterize the fracture behavior of thermally tempered glass. The desired fracture behavior is called "cutting" and occurs when the glass reaches full tempering. The cut threshold of tempered glass is an arbitrarily defined fracture behavior that should be considered "safe" in the event of glass failure. There are some standards in the world, such as ASTM C1048 and ANSI Z97.1 in the United States, EN12150-1 in Europe, GOST 5727-88 in Russia, JIS R 3206 in Japan, and GB 15763.2 in China (all these standards are incorporated by reference) In this article). These standards are almost the same in all countries. For thick glass larger than 3mm, the pieces of tempered soda-lime glass are required to contain at least 30 to 40 pieces (1.6 pieces per square centimeter) in a 50 mm x 50 mm area. ), And in the case of thinner glass, Japanese standards specifically require at least 60 pieces.

Of interest is the ability to predict the glass composition's ability to generate stress during thermal tempering. The simplest approximation that can be made in forming a more general expression is to assume that for any selected combination of glass thickness and quenching rate, the stress due to thermal strain is a fraction of the maximum possible. Therefore, the general expression of the compressive tempering stress formed when quenching from a constant viscosity can be expressed as: Where α ^s is the CTE of glass in solid form, α ^L is the CTE of glass in liquid form, T _soft is the softening point temperature, T _strain is the strain point temperature, and the constant Ψ is the material property called the "tempering capacity parameter". It also represents the maximum thermal strain that can be formed if the surface freezes after quenching. This maximum thermal strain can be roughly estimated by a two-step integration of thermal expansion, which is a function of temperature and general glass properties. It is assumed that the coefficient of thermal expansion (CTE) is constant from room temperature to the strain point, and then constant from the strain point to softening. With this in mind, and assuming room temperature is close to 0 ° C, the more general "tempering capacity parameter" can be expressed as: Where E is expressed in GPa, temperature is given in ° C, and α is expressed in ° C ^-1 . It can be seen that this expression contains a more general form of volume strain calculated using the strain point of the glass between the glassy and liquid representations.

By measuring some standard properties of a given glass, if the constant C (h, t, η) is known, the expected tempering stress can be estimated. This constant has been evaluated using modeling for a wide range of known compositions, and the relative tempering capabilities of various glass compositions can be quickly compared to each other from the calculations of rhenium. When calculating the tempering ability of various glass compositions, the results show that the combination of various properties is sufficient to reach a similar end point, and the huge differences in composition and properties of glass are almost indistinguishable in terms of tempering ability.

The glass disclosed herein has a high coefficient of thermal expansion and a high Young's modulus, and can be used with a thermal tempering process to obtain a more improved tempering compared to commercially available glass. The glass described herein is needed to meet the growing demand for stronger but thinner heat-strengthened glass for commercial electronics, automotive, and architectural applications, where durability and / or scratch resistance are required, and Has a "safe" break pattern. As the glass becomes thinner, it becomes more difficult to generate any thermal tempering stress, and the central tension required to safely "cut" the fracture pattern increases-creating a compounding challenge. The development of glass that produces enhanced tempering stress can help meet this challenge. In addition, these glasses must also maintain significant chemical durability as they may be exposed to elements for long periods of time.

It has been found that glass having a tempering capacity parameter Ψ of 0.8 or higher, 0.85 or higher, or even 0.9 or higher has the ability to increase thermal tempering. In some embodiments, in order to improve the tempering ability, it has been found that the low temperature thermal expansion coefficient (LTCTE) should be 5.5 × 10 ^-7 / ° C or higher. In some embodiments, it has been found that the high temperature thermal expansion coefficient (HTCTE) should be 27 × 10 ^-7 / ° C or higher. In some embodiments, it has been found that, in order to improve the tempering capacity and the sum LTCTE HTCTE should be greater than ^{35x10 -7 / ℃, 37x10 -7 /} ℃ or 40x10 ^-7 / ℃. The invention is a novel glass composition space with high thermal expansion coefficient and Young's modulus. In some embodiments, the glass composition has been found to have improved tempering capabilities when the Young's modulus is greater than 67 GPa and the tempering capability factor is greater than or equal to 0.75 (approximate value of commercially available soda lime glass).

In some embodiments, the glass includes a combination of the following materials: SiO ₂ , Na ₂ O or K ₂ O, Al ₂ O ₃ , B ₂ O ₃ or ZnO, and an alkaline earth oxide. For example, embodiments may include: from 60 mole% to 72 mole% SiO ₂ (60 mole% ≤ SiO ₂ ≤ 72 mole%); from greater than 0 mole% Al ₂ O ₃ (0 mole% < Al ₂ O ₃ ); from more than 0 mole% MgO (0 mole% <MgO); from more than 0 mole% CaO (0 mole% <CaO); 6-16 mole% Na ₂ O + K ₂ O (6 mol% ≤ Na ₂ O + K ₂ O ≤ 16 mol%), 0-16 mol% Na ₂ O (0 mol% ≤ Na ₂ O ≤ 16 mol%); 0-16 mol Ear% K ₂ O (0 mole% ≤ K ₂ O≤ 16 mole%); and one or more of B ₂ O ₃ or ZnO, where B ₂ O ₃ includes 1 when B ₂ O ₃ is present -10 mole% (1 mole% ≤ B ₂ O ₃ ≤ 10 mole%); and when ZnO is present, the ZnO includes 3-8 mole% (3 mole% ≤ ZnO ≤ 8 mole%) . Additional aspects of the various components that can constitute the implemented composition are detailed below.

In some embodiments, the glass includes a combination of the following materials: SiO ₂ , Na ₂ O or K ₂ O, Al ₂ O ₃ , B ₂ O ₃ , and an alkaline earth oxide. For example, embodiments may include: from 60 mole% to 65 mole% SiO ₂ (60 mole% ≤ SiO ₂ ≤ 65 mole%); from 5 mole% to 10 mole% Al ₂ O ₃ (5 mole% ≤ Al ₂ O ₃ ≤ 10 mole%); from 3 mole% to 10 mole% MgO (3 mole% ≤ MgO ≤ 10 mole%); from 5 mole% to 15 moles Ear% CaO (5 mole% ≤ CaO ≤ 15 mole%); 8-15 mole% Na ₂ O + K ₂ O (8 mole% ≤ Na ₂ O + K ₂ O ≤ 15 mole%); 0-15 mole% Na ₂ O (0 mole% ≤ Na ₂ O≤ 15 mole%); 0 mole% to 15 mole% K ₂ O (0 mole% ≤ K ₂ O≤ 15 mole %); And 1.5 mol% to 6 mol% B ₂ O ₃ (1.5 mol% ≤ B ₂ O ₃ ≤ 6 mol%).

Alternative embodiments may include: from 65 mol% to 70 mol% SiO ₂ (65 mol% ≤ SiO ₂ ≤ 70 mol%); from> 0 mol% to 5 mol% Al ₂ O ₃ ( ＞ 0 mole% ≤ Al ₂ O ₃ ≤ 5 mole%); from 4 mole% to 8 mole% MgO (4 mole% ≤ MgO ≤ 8 mole%); from 7 mole% to 11 mole Ear% CaO (7 mole% ≤ CaO ≤ 11 mole%); 9-14 mole% Na ₂ O + K ₂ O (9 mole% ≤ Na ₂ O + K ₂ O ≤ 14 mole%); 0-14 mole% Na ₂ O (0 mole% ≤ Na ₂ O≤ 14 mole%); 0 mole% to 14 mole% K ₂ O (0 mole% ≤ K ₂ O≤ 14 mole) %); And 1 mol% to 6 mol% B ₂ O ₃ (1 mol% ≤ B ₂ O ₃ ≤ 6 mol%).

Still other embodiments may include: from 65 mol% to 70 mol% SiO ₂ (65 mol% ≤ SiO ₂ ≤ 70 mol%); from> 0 mol% to 5 mol% Al ₂ O ₃ (> 0 mole% ≤ Al ₂ O ₃ ≤ 5 mole%); from 5 mole% to 10 mole% MgO (5 mole% ≤ MgO ≤ 10 mole%); from 6 mole% To 13 mole% CaO (6 mole% ≤ CaO ≤ 13 mole%); 10-16 mole% Na ₂ O + K ₂ O (10 mole% ≤ Na ₂ O + K ₂ O ≤ 16 mole %); 2-16 mole% Na ₂ O (2 mole% ≤ Na ₂ O≤ 16 mole%); 0 mole% to 8 mole% K ₂ O (0 mole% ≤ K ₂ O≤ 8 mol%); and 1 mol% to 6 mol% B ₂ O ₃ (1 mol% ≤ B ₂ O ₃ ≤ 6 mol%).

Still other embodiments may include: from 65 mol% to 72 mol% SiO ₂ (65 mol% ≤ SiO ₂ ≤ 72 mol%); from 4 mol% to 10 mol% Al ₂ O ₃ (4 mole% ≤ Al ₂ O ₃ ≤ 10 mole%); from 3 mole% to 10 mole% MgO (3 mole% ≤ MgO ≤ 10 mole%); from> 0 mole% to 13 mol% CaO (0 mol% <CaO ≤ 13 mol%); 10-16 mol% Na ₂ O + K ₂ O (10 mol% ≤ Na ₂ O + K ₂ O ≤ 16 mol% ); 10-16 mole% Na ₂ O (10 mole% ≤ Na ₂ O≤ 16 mole%); 0 mole% to 6 mole% K ₂ O (0 mole% ≤ K ₂ O≤ 6 Molar%); and 1.5 Molar% to 8 Molar% B ₂ O ₃ (1.5 Molar% ≤ B ₂ O ₃ ≤ 8 Molar%).

When SiO ₂ (and Al ₂ O ₃ , B ₂ O ₃ , P ₂ O ₅ , ZrO ₂ and SnO ₂ ) is present in the glass, it is a network-forming agent. SiO ₂ is the largest oxide component of glass and can be incorporated into SiO ₂ to provide high temperature stability and chemical durability. In some embodiments, the glass can include from 60 to 72 mole% SiO ₂ . In some embodiments, the glass can include from 60 to 65 mole% SiO ₂ . In some embodiments, the glass can include from 65 to 72 mole% SiO ₂ . In some embodiments, the glass can include from 65-70 mole% SiO ₂ . In some embodiments, the glass can include from 60 to 72 mol%, 63 to 72 mol%, 65 to 72 mol%, 68 to 72 mol%, 60 to 70 mol%, 63 to 70 mol %, 65 to 70 mole%, 68 to 70 mole%, 60 to 68 mole%, 63 to 68 mole%, 65 to 68 mole%, 60 to 65 mole%, 63 to 65 mole% , Or 60 to 63 mole% of SiO ₂ . In some embodiments, the glass includes 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, or 72 mole% SiO ₂ .

Al ₂ O ₃ can affect the structure of the glass, in addition to reducing the liquidus temperature and the coefficient of thermal expansion, or increasing the strain point. In some embodiments, the glass can include greater than 0 mole% Al ₂ O ₃ . In some embodiments, the glass can include Al ₂ O ₃ from> 0 to 12 mole%. In some embodiments, the glass can include a> 0 to 5 mole%, 4-10 mole%, 5-10 mole% Al ₂ O ₃ or> 0 to 3 mole% Al ₂ O _3. In some embodiments, the glass can include from 0.5 to 4 mole% Al ₂ O ₃ . In some embodiments, the glass can include from> 0 to 12 mole%,> 0 to 10 mole%,> 0 to 8 mole%,> 0 to 6 mole%,> 0 to 4 mole%, > 0 to 2 mole%, 1 to 12 mole%, 1 to 10 mole%, 1 to 8 mole%, 1 to 6 mole%, 1 to 4 mole%, 1 to 2 mole%, 3 to 8 mole%, 3 to 6 mole%, 3 to 10 mole%, 3 to 12 mole%, 5 to 8 mole%, 5 to 10 mole%, 5 to 12 mole%, 7 to 12 mole%, 7-10 mole% or 8-10 mole% Al ₂ O _3. In some embodiments, the glass can include about> 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 mole% Al ₂ O ₃ .

Without being bound by theory, it is believed that the incorporation of B ₂ O ₃ into the glass described herein will affect the coefficient of thermal expansion (especially the coefficient of thermal expansion at high temperatures) and improve the temperability of the glass. In some embodiments, the glass can include 1 mole% to 10 mole% B ₂ O ₃ . In some embodiments, the glass can comprise from 1 mole% to 8 mole%, or from 1 mole% to 6 mole% B ₂ O _3. In some embodiments, the glass can include from about 1.5 to 8 mole% B ₂ O ₃ or 1.5 to 6 mole% B ₂ O ₃ . In some embodiments, the glass can include from 1 to 4 mole% B ₂ O ₃ . In some embodiments, the glass can include from 1 to 10 mole%, 1.5 to 10 mole%, 2 to 10 mole%, 4 to 10 mole%, 1 to 8 mole%, 1.5 to 8 moles. %, 2 to 8 mol%, 4 to 8 mol%, 1 to 6 mol%, 1.5 to 6 mol%, 2 to 6 mol%, 4 to 6 mol%, 1 to 4 mol% , 1.5 to 4 mole%, 2 to 4 mole%, 1.5 to 3 mole%, or 1 to 3 mole% B ₂ O ₃ . In some embodiments, the glass can include about 0,> 0, 1, 2, 3, 4, or 5 mole% B ₂ O ₃ .

Zinc oxide (ZnO) may be present and the zinc oxide affects the properties of the glass, including Young's coefficient. In some embodiments, the glass can include 3 to 8 mole% of ZrO ₂ when ZnO is present, or in some embodiments, from 3 to 5 mole% of ZnO. In some embodiments, the glass can include 3, 4, 5, 6, 7, or 8 mole% ZnO.

Without wishing to be bound by theory, it is believed that in some embodiments, both ZnO and B ₂ O ₃ may have similar effects on material properties. In some embodiments, the glass is free of ZnO when B ₂ O ₃ is present in the glass. Alternatively, in some embodiments, when ZnO is present in the glass, the glass is free of B ₂ O ₃ .

Alkaline earth oxides can improve desired properties in materials, including affecting Young's modulus and coefficient of thermal expansion. In some embodiments, the glass can include from> 0 mol% to about 20 mol% MO (0 mol% ≤ MO ≤ 20 mol%), where M is an alkaline earth group metal Mg, Ca, Sr, And the sum of Ba. In some embodiments, the glass can include from> 0 to 18 mole% MO. In some embodiments, the glass can include from> 0 to 16 mole% MO. In some embodiments, the glass can include about> 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 , Or 20 mol% MO.

In some embodiments, the glass can include MgO, CaO, or SrO. In some embodiments, the glass can include greater than 0 mole% MgO. In some embodiments, the glass can include from> 0 to 10 mole% MgO. In some embodiments, the glass can include from 3 to 10 mole%, 5 to 10 mole%, and 5 to 8 mole% MgO. In some embodiments, the glass can include from> 0 to 10 mole%,> 0 to 8 mole%,> 0 to 6 mole%,> 0 to 4 mole%,> 0 to 2 mole%, 1 to 10 mole%, 1 to 8 mole%, 1 to 6 mole%, 1 to 4 mole%, 1 to 2 mole%, 3 to 8 mole%, 3 to 6 mole%, 3 To 10 mole%, 5 to 8 mole%, 5 to 10 mole%, 7 to 10 mole%, or 8 to 10 mole% MgO. In some embodiments, the glass can include about> 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mole% MgO.

In some embodiments, the glass can include greater than 0 mole% CaO. In some embodiments, the glass can include from> 0 to 15 mole% CaO. In some embodiments, the glass can include from> 0 to 5 mole%, 6 to 13 mole%, 5 to 15 mole%, 7 to 13 mole%, 7 to 11 mole%, 8 to 12 moles. Ear% CaO. In some embodiments, the glass can include from> 0 to 15 mole%,> 0 to 13 mole%,> 0 to 11 mole%,> 0 to 9 mole%,> 0 to 7 mole%, > 0 to 5 mole%, 1 to 15 mole%, 1 to 13 mole%, 1 to 11 mole%, 1 to 9 mole%, 1 to 7 mole%, 1 to 5 mole%, 3 to 15 mole%, 3 to 13 mole%, 3 to 11 mole%, 3 to 9 mole%, 3 to 7 mole%, 3 to 5 mole%, 5 to 15 mole%, 5 To 13 mole%, 5 to 11 mole%, 5 to 9 mole%, 5 to 7 mole%, 7 to 15 mole%, 7 to 13 mole%, 7 to 11 mole%, 7 to 9 mol%, 9 to 15 mol%, 9 to 13 mol%, 9 to 11 mol%, 11 to 15 mol%, or 11 to 13 mol% CaO. In some embodiments, the glass can include about> 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 mole% CaO.

SrO may be present in some embodiments, and in such embodiments, the glass can include from 0 to 5 mole% SrO. In some embodiments, the glass can include from> 0 to 5 mole% SrO. In some embodiments, the glass can include from about> 0 to 3.5 mole% SrO or 0.2 to 3 mole% SrO. In some embodiments, the glass can include from 1 to 4 mole% SrO. In some embodiments, the glass can include from 0.2 to 5 mole%, 0.2 to 4 mole%, 0.2 to 3 mole%, 0.2 to 2 mole%,> 0 to 5 mole%,> 0 to 4 Mole%,> 0 to 3 Mole%,> 0 to 2 Mole%, 1 to 5 Mole%, 1 to 4 Mole%, or 1 to 3 Mole% SrO. In some embodiments, the glass can include about 0,> 0, 1, 2, 3, 4, or 5 mole% SrO.

Na ₂ O and K ₂ O can improve the tempering ability of glass and affect the thermal expansion coefficient especially at low temperature. In some embodiments, the glass can include from 0 to 16 mole% Na ₂ O. In some embodiments, the glass can include> 0 to 15 mole% Na ₂ O. In some embodiments, the glass can include 10 to 16 mole% Na ₂ O. In some embodiments, the glass can include 2 to 16 mole% Na ₂ O. In some embodiments, the glass can include from 0 to 16 mol%, 0 to 15 mol%, 0 to 14 mol%, 0 to 10 mol%, 0 to 8 mol%, 0 to 5 mol. %,> 0 to 16 mole%,> 0 to 15 mole%,> 0 to 14 mole%,> 0 to 10 mole%,> 0 to 8 mole%,> 0 to 5 mole%, 2 to 16 mole%, 2 to 15 mole%, 2 to 14 mole%, 2 to 10 mole%, 2 to 8 mole%, 2 to 5 mole%, 5 to 16 mole%, 5 To 15 mol%, 5 to 14 mol%, 5 to 10 mol%, 5 to 8 mol%, 8 to 16 mol%, 8 to 15 mol%, 8 to 14 mol%, 8 to 10 mole%, 10 to 16 mole%, 10 to 15 mole%, or 10 to 14 mole% Na ₂ O. In some embodiments, the glass can include 0,> 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 mole% Na ₂ O.

In some embodiments, the glass can include from 0 to 16 mole% K ₂ O. In some embodiments, the glass can include> 0 to 15 mole% K ₂ O. In some embodiments, the glass can include 0 to 8 mole% K ₂ O. In some embodiments, the glass can include 0 to 6 mole% K ₂ O. In some embodiments, the glass can include from 0 to 16 mol%, 0 to 15 mol%, 0 to 14 mol%, 0 to 10 mol%, 0 to 8 mol%, 0 to 5 mol. %,> 0 to 16 mole%,> 0 to 15 mole%,> 0 to 14 mole%,> 0 to 10 mole%,> 0 to 8 mole%,> 0 to 5 mole%, 2 to 16 mole%, 2 to 15 mole%, 2 to 14 mole%, 2 to 10 mole%, 2 to 8 mole%, 2 to 5 mole%, 5 to 16 mole%, 5 To 15 mol%, 5 to 14 mol%, 5 to 10 mol%, 5 to 8 mol%, 8 to 16 mol%, 8 to 15 mol%, 8 to 14 mol%, 8 to 10 mole%, 10 to 16 mole%, 10 to 15 mole%, or 10 to 14 mole% K ₂ O. In some embodiments, the glass can include 0,> 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 mole% K ₂ O.

In some embodiments, the total amount of base Na ₂ O and K ₂ O is important for glass properties. In some embodiments, the glass can include 6 to 16 mole% Na ₂ O + K ₂ O. In some embodiments, the glass can include 8 to 16 mole% Na ₂ O + K ₂ O. In some embodiments, the glass can include 8 to 15 mole% Na ₂ O + K ₂ O. In some embodiments, the glass can include 10 to 16 mole% Na ₂ O + K ₂ O. In some embodiments, the glass can include 9 to 14 mole% Na ₂ O + K ₂ O. In some embodiments, the glass can include from 6 to 16 mole%, 8 to 16 mole%, 10 to 16 mole%, 6 to 15 mole%, 8 to 15 mole%, 10 to 15 moles. %, 6 to 14 mol%, 8 to 14 mol%, 10 to 14 mol%, 6 to 12 mol%, 8 to 12 mol%, 10 to 12 mol%, 6 to 10 mol% , 8 to 10 mole%, or 6 to 8 mole% Na ₂ O + K ₂ O. In some embodiments, the glass can include 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 mole% Na ₂ O + K ₂ O.

Na ₂ O can be used in glass for ion exchange and chemical tempering. In some embodiments, the glass can comprise from 0 to about 5 mole% mole% Na ₂ O (0 mole% ≤ Na ₂ O ≤ 5 mole%). In some embodiments, the glass can include from greater than 0 to 5 mole% Na ₂ O. In some embodiments, the glass can include from about 0 to 3 mole% Na ₂ O or> 0 to 3 mole% Na ₂ O. In some embodiments, the glass can include from 0.5 to 4 mole% Na ₂ O. In some embodiments, the glass can include from 0 to 5 mole%, 0 to 4 mole%, 0 to 3 mole%, 0 to 2 mole%,> 0 to 5 mole%,> 0 to 4 Mole%,> 0 to 3 Mole%,> 0 to 2 Mole%, 1 to 5 Mole%, 1 to 4 Mole%, or 1 to 3 Mole% Na ₂ O. In some embodiments, the glass can include about 0,> 0, 1, 2, 3, 4, or 5 mole% Na ₂ O.

K ₂ O can also be used for ion exchange and can be present in glass in amounts ranging from 0 mole% to about 10 mole% K ₂ O (0 mole% ≤ K ₂ O ≤ 10 mole%). In some embodiments, the glass can include from> 0 to 10 mole% K ₂ O. In some embodiments, the glass can comprise from about 0 to 5 mole% K ₂ O or> 0 to 3 mole% K ₂ O. In some embodiments, the glass can include from 0.5 to 4 mole% K ₂ O. In some embodiments, the glass can include from 0 to 10 mole%, 0 to 8 mole%, 0 to 5 mole%, 0 to 4 mole%, 0 to 3 mole%,> 0 to 10 moles. Ear%,> 0 to 8 Mol%,> 0 to 5 Mol%,> 0 to 3 Mol%, 1 to 10 Mol%, 1 to 8 Mol%, 1 to 5, 1 to 4 Mol %, 1 to 3 mole%, 2 to 10 mole%, 2 to 8 mole%, or 2 to 4 K ₂ O. In some embodiments, the glass can include about 0,> 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mole% K ₂ O.

Alkaline earth oxides can provide the advantages of ion exchange in glass and improve other properties in materials. In some embodiments, the glass can include from 0 mol% to about 10 mol% MO (0 mol% ≤ MO ≤ 10 mol%), where M is an alkaline earth group metal Mg, Ca, Sr, and The sum of Ba. In some embodiments, the glass can include from 0 to 8 mole% MO. In some embodiments, the glass can include from 0 to 5 mole% MO. In some embodiments, the glass can include from 1 to 8 mole% MO. In some embodiments, the glass can include from 0 to 10 mole%, 0 to 8 mole%, 0 to 6 mole%, 0 to 4 mole%, 1 to 10 mole%, and 1 to 8 moles. %, 1 to 6 mole%, 2 to 10 mole%, 2 to 8 mole%, or 2 to 6 mole% MO. In some embodiments, the glass can include about> 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mole% MO.

In some embodiments, the glasses above further include a coloring component. The coloring component may include, for example, Fe ₂ O ₃ , V ₂ O ₅ , Cr ₂ O ₃ , TiO ₂ , MnO ₂ , NiO, ZnO, CuO, NiO, Co ₃ O ₄ , rare earth oxides, and the above materials. combination. In some examples, the total mole% of the coloring component is from 0 to 4 mole%, 0 to 3 mole%, 0 to 2 mole%, 0 to 1 mole%,> 0 to 0.1,> 0 to 0.5 ,> 0 to 1,> 0 to 2,> 0 to 3, or> 0 to 4 mole%.

Additional ingredients may be incorporated into the glass to provide additional benefits, or the additional ingredients may be incorporated as impurities that are typically found in commercially prepared glasses. For example, additional ingredients can be added as a fining agent and / or for other purposes, such as to help remove gaseous inclusions from a molten batch used to produce glass. In some embodiments, the glass can include one or more compounds that can be used as ultraviolet radiation absorbers. In some embodiments, the glass can include 3 mol% or less of MnO, Nb ₂ O ₅ , MoO ₃ , Ta ₂ O ₅ , WO ₃ , SnO ₂ , Fe ₂ O ₃ , As ₂ O ₃ , Sb ₂ O ₃ , Cl, Br, or a combination thereof. In some embodiments, the glass can include from 0 to about 3 mole%, 0 to about 2 mole%, 0 to about 1 mole%, 0 to 0.5 mole%, 0 to 0.1 mole%, 0 to 0.05 mol%, or 0 to 0.01 mol% of MnO, ZnO, Nb ₂ O ₅ , MoO ₃ , Ta ₂ O ₅ , WO ₃ , SnO ₂ , Fe ₂ O ₃ , As ₂ O ₃ , Sb ₂ O ₃ , Cl, Br, or a combination of the above materials. In some embodiments, the glass can include from 0 to about 3 mole%, 0 to about 2 mole%, 0 to about 1 mole%, 0 to about 0.5 mole%, 0 to about 0.1 mole%, 0 to about 0.05 mole%, or from 0 to about 0.01 mole% of SnO ₂ or Fe ₂ O _3, or combinations of the aforementioned materials. According to some embodiments, the glasses can also include various impurities associated with the batch and / or introduced into the glass through melting, clarification, and / or forming equipment used to produce the glass.

Non-limiting examples of precursor glass used to form the implemented glass are listed in Table 1, where the values of these ingredients are listed in mole%. Table 1 Table 1 (continued) Table 1 (continued) Table 1 (continued)

In addition to having high fracture toughness, the glasses described herein can possess color and transparency / translucency properties, making them useful for many applications. The glass of one or more embodiments may exhibit substantially white, white transparent, gold, or amber, or other colors. In some embodiments, the glasses exhibit colors in SCE color space coordinates (determined from the reflection spectrum measurement using a spectrophotometer, excluding the luminous body D65 and specular reflection), and the range is as follows: a * = from about -5 About -1; b * = from about 5 to about 18; and L *> 83. In some applications, these glasses are transparent and quantitatively white to yellow-brown in color, and receive particular attention in photovoltaic applications.

Color samples are shown in Table 2 . The first four columns of the table have the color coordinates of the thin-line PV cells and the color coordinates when the glass is on top of the PV cells (glass thickness is 2mm or 4mm). The last four columns are the color coordinates of the glass itself. Where L * indicates brightness, a * is the red / green coordinate, and b * is the yellow / blue coordinate. The Δ values (ΔL *, Δa *, Δb *) of L *, a *, b * can be positive (+) or negative (-). In terms of specular reflection exclusion (SCE) color coordinates, all glass makes the PV cells darker and shifts the color to less red and less blue. When combined with PV cells, a less blue color is more aesthetically desirable for appearance.

As shown in Table 1, for all glasses, the transmittance of visible light (390 to 700 nm) exceeds 60%, and approximately 80% is in the middle (about 550 nm). Generally, solar cells are made of N-type and P-type semiconductor materials, which use visible light wavelengths from 380nm to 750nm to generate electricity. Therefore, these glasses with the implemented color components (for example, the darkest color is composition Z, 4 mm) will not significantly reduce the efficiency of the solar cell. Exhibit 1

In some embodiments, the glass can be strengthened to include a compressive stress (CS) extending from a surface of the glass to a depth of compression (DOC). These compressive stress regions are balanced by a central portion where tensile stresses appear. In DOC, stress spans from positive (compressive) stress to negative (tensile) stress.

As an alternative to thermal tempering, the glass disclosed herein may be ion exchanged by immersion in at least one ion exchange bath containing molten salts of at least one alkali metal, such as lithium, sodium, or potassium ( Such as nitrates, sulfides, halides, or the like). Ion exchange is commonly used in chemically strengthened glass. In a specific example, alkali cations in such a source of cations (eg, molten salt baths, or "ion exchange" baths) are exchanged with smaller alkali cations in the glass to achieve the Layer, which extends from the glass surface to the depth of compression (DOC) within the glass phase. For example, potassium ions from a cation source are usually exchanged for sodium and / or lithium ions in the glass phase, and the K ⁺ concentration profile is related to compressive stress and layer depth. The ion exchange bath may contain salts (or multiple salts) of a single alkali metal (eg, sulfides, nitrates, or halides of Li, Na, or K), or salts of two or more alkali metals (Such as lithium and sodium sulfides, nitrates, or halides, or sodium and potassium sulfides, nitrates, or halides). Ion exchange is performed in an ion exchange bath at a temperature of about 390 ° C to about 550 ° C for a time ranging from about 0.5 hours to about 24 hours.

In some embodiments, the glass is ion exchanged and has a compression layer extending from the surface to a depth of compression (DOC), the compression depth being at least about 10 μm; or, in some embodiments, the compression layer enters the glass for at least about 30 μm, or in some embodiments, measured in thickness (surface-to-center), up to about 10%, 15%, 20%, or 25% into the glass. In some embodiments, the compression layer extends from the glass surface to a depth of up to about 20% of the glass thickness. In some embodiments, the glass may be strengthened to exhibit surface compressive stresses ranging from 250 MPa to 800 MPa (or greater).

In tempered glass, the depth of the compression layer can be measured by electron probes, glow discharge emission spectroscopy (GDOES), a technology used to measure solid samples by detecting emissions from atoms contained in the plasma due to sputtering Depth distribution curve of the constituent elements), or similar techniques, which should provide depth-dependent composition data, where the data will show the incorporation of potassium and / or sodium at the surface (where Na ⁺ replaces the glass phase Li ⁺ ). The DOC of the precursor glass can be measured by a surface stress meter (FSM) using a commercially available instrument such as FSM-6000 manufactured by Orihara Industries, Japan. Surface stress measurement relies on the accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. SOC is instead measured by methods known in the art, such as the fiber and four-point bending methods, both of which are described in ASTM Standard C770-98 (2013) and titled "Standard Test Method for Glass Stress Measurement- "Optical Coefficient", the content of which is incorporated herein by reference in its entirety; in addition, it can also be measured by the block cylinder method. CS can also be measured through FSM. As used herein, CS may be the "maximum compressive stress", which is the highest compressive stress value measured within the compressive stress layer. In some embodiments, the maximum compressive stress is on the glass surface. In other embodiments, the maximum compressive stress may occur at a depth below the surface, giving the compression profile a "embedded peak" appearance.

The thermally or chemically strengthened glass or article disclosed herein may be incorporated into another article, such as an article (or display article) with a display (eg, consumer electronics, including mobile phones, tablets, computers, navigation systems , And the like), construction products (e.g. windows, skylights, roof panels), transportation products (e.g. cars, trains, airplanes, sea liners, etc.), household products, or anything that would benefit from transparency, scratch resistance, Abrasion-resistant products, or a combination of the above. In other embodiments, the glass forms part of a consumer electronics product, such as a cell phone or smartphone, a laptop computer, a tablet computer, or the like. Such consumer electronic products generally include a housing having a front surface, a rear surface, and a side surface, and the product includes electronic components such as a power supply, a controller, a memory, a display, and the like, the components being located at least partially Inside the enclosure. In some embodiments, the glass described herein includes at least a portion of a protective element, such as, but not limited to, a housing and / or display of a consumer electronics product. The process of making glass

Glasses with the oxide contents listed in Table 1 can be prepared by conventional methods. For example, in some embodiments, the precursor glass may be formed by thoroughly mixing the necessary batch materials (eg, using a turbulent mixer) to ensure a homogeneous melt, and then put in silicon dioxide and / or Platinum crucible. The crucible can be placed in a hot furnace and the glass batch can be melted and maintained at a temperature ranging from 1250 to 1650 ° C for a time of about 6-16 hours. The melt can then be poured into a steel mold to produce a glass slab. These slabs can then be immediately transferred to an annealer operating at about 500 to 650 ° C, where the glass is held at this temperature for about 1 hour, and then cooled overnight. In another non-limiting example, precursor glass is prepared by dry blending an appropriate oxide and mineral source for a sufficient time to thoroughly mix the ingredients. The glass was melted in a platinum crucible at a temperature of about 1100 ° C to about 1650 ° C and held at this temperature for about 16 hours. Subsequently, the obtained glass melt was poured on a steel table and cooled. The precursor glass is then annealed at a suitable temperature.

The tempering of the implemented glass is achieved using conventional processes, where the glass is heated to a predetermined temperature in a radiant heat furnace or a convection heat furnace (or a "combined mode" furnace using both technologies), and the gas is then Cooling ("quenching") is generally performed by convection by blowing a large amount of ambient air against or along the glass surface. example

Implemented glass can be made as described herein. The properties of Glaverbel soda-lime glass (SLG) were compared with the properties of the glass implemented. The properties of the glass are shown in Table 1 . In addition, Table 3 compares the surface compression composition C with Glaverbel SLG with respect to a 1-mm-thick glass slab. Under comparable tempering conditions, Composition C exhibited a tempering ability of 0.99, which is about 32% higher than SLG, and was able to achieve a surface compression of 145 MPa, compared to 105 MPa for SLG. Table 2

Although a typical embodiment has been proposed for the purpose of illustration, the foregoing description should not be regarded as limiting the scope of the content disclosed in this case or the scope of the attached patent application. Therefore, without departing from the spirit and scope of the disclosure of the present case or the scope of the attached patent application, those with ordinary knowledge in the technical field to which the invention pertains can think of various modifications, adaptations, and alternatives.

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Claims (30)

A glass composition comprising: 60 to 72 mole% SiO ₂ ; Al ₂ O ₃ greater than 0 mole%; MgO greater than 0 mole%; CaO greater than 0 mole%; 6 to 16 mole% Na ₂ O + K ₂ O; 0 to 16 mole% Na ₂ O; 0 to 16 mole% K ₂ O; and one or more of B ₂ O ₃ or ZnO ₂ , where: when B ₂ When O _{3 is} present, it includes 1 to 10 mol% of B ₂ O ₃ ; and when ZnO is present, it includes 3 to 8 mol% of ZnO. The glass composition according to claim 1, comprising> 0 to 10 mole% MgO. The glass composition according to claim 1, comprising> 0 to 12 mole% Al ₂ O ₃ . The glass composition according to claim 1, comprising> 0 to 15 mol% of CaO. The glass composition according to claim 1, comprising 8 to 16 mole% Na ₂ O + K ₂ O. The glass composition according to claim 1, comprising> 0 to 15 mole% Na ₂ O. The glass composition according to claim 1, comprising 1.5 to 8 mole% of B ₂ O ₃ and being free of ZnO. The glass composition according to claim 1, comprising 3 to 8 mole% of ZnO and being free of B ₂ O ₃ . The glass composition according to claim 1, wherein the glass composition has a low-temperature thermal expansion coefficient (LTCTE) measured at 25 ° C and a high-temperature thermal expansion coefficient (HTCTE) measured at 300 ° C, and wherein the LTCTE and the HTCTE The total is 35x10 ^-7 / ° C or greater. The glass composition according to claim 9, wherein the sum of the LTCTE and the HTCTE is 37x10 ^-7 / ° C or more. The glass composition according to claim 9, wherein the sum of the LTCTE and the HTCTE is 40x10 ^-7 / ° C or more. The glass composition according to claim 1, wherein the glass composition has a temperability ψ, and the tempering ability ψ is equal to or greater than 0.80. The glass composition according to claim 12, wherein the tempering capacity ψ is equal to or greater than 0.85. The glass composition according to claim 12, wherein the tempering capacity ψ is equal to or greater than 0.90. The glass composition according to claim 1, comprising: 60 to 65 mole% SiO ₂ ; 5 to 10 mole% Al ₂ O ₃ ; 3 to 10 mole% MgO; 5 to 15 mole% CaO; 8 to 15 mole% Na ₂ O + K ₂ O; 0 to 15 mole% Na ₂ O; 0 to 15 mole% K ₂ O; and 1.5 to 6 mole% B ₂ O ₃ , wherein the glass composition has a low-temperature thermal expansion coefficient (LTCTE) measured at 25 ° C and a high-temperature thermal expansion coefficient (HTCTE) measured at 300 ° C, wherein the sum of the LTCTE and the HTCTE is 35x10 ^-7 / ° C Or greater; and the glass composition has a tempering ability ψ, and the tempering ability ψ is equal to or greater than 0.80. The glass composition according to claim 15, wherein the sum of the LTCTE and the HTCTE is 40x10 ^-7 / ° C or more. The glass composition according to claim 15, wherein the tempering capacity ψ is equal to or greater than 0.90. The glass composition according to claim 1, comprising: 65 to 72 mole% SiO ₂ ; 4 to 10 mole% Al ₂ O ₃ ; 3 to 10 mole% MgO;> 0 to 5 mole % of CaO; 10 to 16 mole% of _{Na 2 O + K 2 O;} 10 to 16 mole% of Na ₂ O; 0 to 10 mole% of K ₂ O; and 1.5 to 8 mole% of B ₂ O ₃ , wherein the glass composition has a low-temperature thermal expansion coefficient (LTCTE) measured at 25 ° C and a high-temperature thermal expansion coefficient (HTCTE) measured at 300 ° C, wherein the sum of the LTCTE and the HTCTE is 40x10 ^-7 / ° C or more; and the glass composition has a tempering ability ψ, and the tempering ability ψ is equal to or greater than 0.80. The glass composition according to claim 18, wherein the tempering capacity ψ is equal to or greater than 0.90. The glass composition according to claim 1, comprising: 65 to 70 mole% SiO ₂ ;> 0 to 5 mole% Al ₂ O ₃ ; 5 to 10 mole% MgO; 6 to 13 mole % CaO; 10 to 16 mole% Na ₂ O + K ₂ O; 2 to 16 mole% Na ₂ O; 0 to 8 mole% K ₂ O; 1 to 6 mole% B ₂ O ₃ ; and wherein the glass composition has a low-temperature thermal expansion coefficient (LTCTE) measured at 25 ° C and a high-temperature thermal expansion coefficient (HTCTE) measured at 300 ° C, wherein the sum of the LTCTE and the HTCTE is 40x10 ^-7 / ° C or more; and the glass composition has a tempering ability ψ, and the tempering ability ψ is equal to or greater than 0.80. The glass composition according to claim 20, wherein the tempering capacity ψ is equal to or greater than 0.90. The glass composition according to claim 1, comprising: 65 to 70 mole% SiO ₂ ;> 0 to 5 mole% Al ₂ O ₃ ; 4 to 8 mole% MgO; 7 to 11 mole % of CaO; 9 to 14 mole% of _{Na 2 O + K 2 O;} 0 to 14 mole% of Na ₂ O; 0 to 14 mole% of K ₂ O; 1. 6 to mole% of B ₂ O ₃ ; and wherein the glass composition has a low-temperature thermal expansion coefficient (LTCTE) measured at 25 ° C and a high-temperature thermal expansion coefficient (HTCTE) measured at 300 ° C, wherein the sum of the LTCTE and the HTCTE is 35x10 ^-7 / ° C or more; and the glass composition has a tempering ability ψ, and the tempering ability ψ is equal to or greater than 0.80. The glass composition according to claim 22, wherein the tempering capacity ψ is equal to or greater than 0.90. The glass composition according to claim 22, wherein the sum of the LTCTE and the HTCTE is 37x10 ^-7 / ° C or more. The glass composition according to claim 22, wherein the sum of the LTCTE and the HTCTE is 40x10 ^-7 / ° C or more. The glass composition according to claim 1, further comprising: a coloring component. The glass composition according to claim 26, wherein the coloring component comprises: Fe ₂ O ₃ , V ₂ O ₅ , Cr ₂ O ₃ , TiO ₂ , MnO ₂ , NiO, ZnO, CuO, NiO, Co ₃ O ₄ , Or a combination of the above. The glass composition according to claim 26, wherein the total mole% of the coloring component is from 0 to 4 mole%. The glass composition according to claim 26, wherein the glass composition exhibits a color, and the color is represented by SCE color space coordinates and has the following values: a * = from about -5 to about -1; b * = From about 5 to about 18; and L *> 83. The glass composition according to claim 26, wherein when the glass composition is rolled into a 2 mm thick slab, the glass composition has a transmittance, and wherein the transmittance is greater than 575 nm 80%.